Polymerization catalysts and processes

ABSTRACT

Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.

This application is a division of application Ser. No. 08/217,469, filedMar. 24, 1994, now U.S. Pat. No. 5,360,879, which is a division ofapplication Ser. No. 08/023,746, filed Feb. 26, 1993, now U.S. Pat. No.5,340,785, which is a file wrapper continuation of application Ser. No.07/809,777, filed Dec. 18, 1991, now abandoned.

BACKGROUND

This invention relates to olefin polymerization, polymerization catalystsystems, and processes to prepare polymerization catalyst systems.

Supported chromium catalysts have long been a dominant factor in theproduction of olefin polymers, such as polyethylene. Chromium-containingcompounds, either supported or unsupported, can also be used tooligomerize olefins. Unfortunately, the production ofchromium-containing compounds for use in catalyst systems, usuallyresults in some waste product which contains chromium compounds.Chromium-containing compounds are and have been considered environmentaland animal toxins for the past several decades. Therefore, elimination,reduction, or utilization of recyclable chromium-containing compounds isdesirable.

SUMMARY OF THE INVENTION

Therefore, it is an object of this invention to provide a process torecycle chromium-containing compounds.

It is a further object of this invention to provide novel polymerizationcatalyst systems.

It is yet another object of this invention to provide a novel processfor preparing supported olefin polymerization catalyst systems.

It is still a further object of this invention to provide novel olefinpolymerization processes.

In accordance with one embodiment of this invention, previously used,such as, for example, spent, chromium compounds comprising a chromiumsource, a pyrrole-containing compound, a metal alkyl and an unsaturatedhydrocarbon are supported on an inorganic oxide support. The resultant,supported chromium compound is calcined to produce an activepolymerization catalyst system, wherein at least a portion of thechromium compound is in a hexavalent state. In accordance with thesecond embodiment of this invention, previously used, such as, forexample, spent, inorganic oxide supported chromium pyrrolide-basedcatalyst and/or waste systems can be calcined to produce an activepolymerization catalyst system. Optionally, the previously used,supported chromium pyrrolide can be re-contacted, i.e., re-impregnated,with additional chromium compound prior to calcination.

In accordance with still another embodiment of the invention, thesenovel catalyst system compositions can be used to polymerize olefins.

DETAILED DESCRIPTION OF THE INVENTION Supports

Catalyst supports useful in this invention can be any conventionalpolymerization catalyst support. Preferably, the catalyst supportcomprises a zeolite or one or more refractory metal inorganic oxides.Exemplary refractory metal inorganic oxide catalyst supports include,but are not limited to, inorganic oxides, either alone or incombination, phosphated inorganic oxides and mixtures thereof.Particularly preferred inorganic oxide supports are selected from thegroup consisting of silica, silica-alumina, alumina, fluorided alumina,silated alumina, thoria, aluminophosphate, aluminum phosphate,phosphated silica, phosphated alumina, silica-titania, preprecipitatedsilica/titania, fluorided/silated alumina and mixtures thereof.Furthermore, any one or more of these supports can contain chromium. Asused in this disclosure, the term "support" is not necessarily limitedto a catalytically inert material. It is possible that the support cancontribute to the activity of the entire catalyst system.

The catalyst supports can be prepared in accordance with any methodknown in the art. Exemplary support method preparations are given inU.S. Pat. Nos. 3,887,494; 3,900,457; 4,053,346; 4,294,724; 4,392,990;4,405,501; and 4,364,855, hereinafter incorporated by reference.Presently, the most preferred catalyst support, because of the greatestcatalytic activity and selectivity, is aluminophosphate, as disclosed inU.S. Pat. No. 4,364,855 (1982).

Chromium Compounds

Waste chromium compounds, prepared in accordance with one embodiment ofthis invention, which previously have been used, comprise a chromiumsource, a pyrrole-containing compound and a metal alkyl, which have beencontacted and/or reacted in the presence of an unsaturated hydrocarbon.Such compounds can have usefulness for other purposes and, as used inthis disclosure, after these chromium compounds have been used at leastonce, for another purpose, these chromium compounds are considered wastechromium compounds. The chromium source can be one or more inorganiccompounds, wherein the chromium oxidation state is from 0 to 6.Generally, the chromium source will have a formula of CrX_(n), wherein Xcan be the same or different and can be any organic or inorganicradical, and n is an integer from 1 to 6. Exemplary organic radicals canhave from about 1 to about 20 carbon atoms per radical, and are selectedfrom the group consisting of alkyl, alkoxy, ester, ketone, and/or amidoradicals. The organic radicals can be straight-chained or branched,cyclic or acyclic, aromatic or aliphatic, can be made of mixedaliphatic, aromatic, and/or cycloaliphatic groups. Exemplary inorganicradicals include, but are not limited to halides, sulfates, and/oroxides.

Preferably, the chromium source is a chromium(II)- and/orchromium(III)-containing compound which can yield a catalyst system withimproved polymerization activity. Most preferably, the chromium sourceis a chromium(III) compound because of ease of use, availability, andenhanced catalyst system activity. Exemplary chromium(III) compoundsinclude, but are not limited to, chromium carboxylates, chromiumnaphthenates, chromium halides, chromium pyrrolides, and/or chromiumdionates. Specific exemplary chromium(III) compounds include, but arenot limited to, chromium(III) 2,2,6,6,-tetramethylheptanedionate[Cr(TMHD)₃ ], chromium(III) 2-ethylhexanoate [Cr(EH)₃ ], chromium(III)naphthenate [Cr(Np)₃ ], chromium(III) chloride, chromium(III)tris(2-ethylhexanoate), chromic bromide, chromic chloride, chromicfluoride, chromium(III) oxy-2-ethylhexanoate, chromium(III)dichloroethylhexanoate, chromium(III) acetylacetonate, chromium(III)acetate, chromium(III) butyrate, chromium(III) neopentanoate,chromium(III) laurate, chromium(III) stearate, chromium (III) pyrrolidesand/or chromium(III) oxalate.

Specific exemplary chromium(II) compounds include, but are not limitedto, chromous bromide, chromous fluoride, chromous chloride, chromium(II)bis(2-ethylhexanoate), chromium(II) acetate, chromium(II) butyrate,chromium(II) neopentanoate, chromium(II) laurate, chromium(II) stearate,chromium(II) oxalate and/or chromium(II) pyrrolides.

The pyrrole-containing compound can be any pyrrole-containing compoundthat will react with a chromium source to form a chromium pyrrolidecomplex. As used in this disclosure, the term"pyrrole-containing-compound" refers to hydrogen pyrrolide, i.e.,pyrrole, (C₄ H₄ N or C₄ H₄ NH), derivatives of hydrogen pyrrolide,substituted pyrrolides, as well as metal pyrrolide complexes. A"pyrrolide" is defined as a compound comprising a 5-membered,nitrogen-containing heterocycle, such as for example, pyrrole,derivatives of pyrrole, and mixtures thereof. Broadly, thepyrrole-containing compound can be pyrrole and/or any heteroleptic orhomoleptic metal complex or salt, containing a pyrrolide radical, orligand. The pyrrole-containing compound can be either affirmativelyadded to the reaction, or generated in-situ.

Generally, the pyrrole-containing compound will have from about 1 toabout 20 carbon atoms per molecule. Exemplary pyrrolides are selectedfrom the group consisting of hydrogen pyrrolide (pyrrole), lithiumpyrrolide, sodium pyrrolide, potassium pyrrolide, cesium pyrrolide,and/or the salts of substituted pyrrolides, because of high reactivityand activity with the other reactants. Examples of substitutedpyrrolides include, but are not limited to, pyrrole-2-carboxylic acid,2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydroindole,2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole,3-acetyl-2,4-dimethylpyrrole,ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrole-proprionate,ethyl-3,5-dimethyl-2-pyrrolecarboxylate. When the pyrrole-containingcompound contains chromium, the resultant chromium compound can becalled a chromium pyrrolide.

The most preferred pyrrole-containing compounds used in a trimerizationcatalyst system, prepared in accordance with this invention, areselected from the group consisting of hydrogen pyrrolide, i.e., pyrrole(C₄ H₅ N), 2,5-dimethylpyrrole and/or chromium pyrrolides. Optionally,for ease of use, a chromium pyrrolide can provide both the chromiumsource and the pyrrole-containing compound. As used in this disclosure,when a chromium pyrrolide is used to form a catalyst system, a chromiumpyrrolide is considered to provide both the chromium source and thepyrrole-containing compound. While all pyrrole-containing compounds canproduce catalyst systems with high activity and productivity, use ofpyrrole and/or 2,5-dimethylpyrrole can produce a catalyst system withenhanced activity and selectivity to a desired product.

The metal alkyl can be any heteroleptic or homoleptic metal alkylcompound. One or more metal alkyls can be used. The alkyl ligand(s) onthe metal can be aliphatic and/or aromatic. Preferably, the alkylligand(s) are any saturated or unsaturated aliphatic radical. The metalalkyl can have any number of carbon atoms. However, due to commercialavailability and ease of use, the metal alkyl will usually comprise lessthan about 70 carbon atoms per metal alkyl molecule and preferably lessthan about 20 carbon atoms per molecule. Exemplary metal alkyls include,but are not limited to, alkylaluminum compounds, alkylboron compounds,alkylmagnesium compounds, alkylzinc compounds and/or alkyl lithiumcompounds. Exemplary metal alkyls include, but are not limited to,n-butyl lithium, s-butyllithium, t-butyllithium, diethylmagnesium,diethylzinc, triethylaluminum, trimethylaluminum, triisobutylalumium,and mixtures thereof.

Preferably, the metal alkyl is selected from the group consisting ofnon-hydrolyzed, i.e., not pre-contacted with water, alkylaluminumcompounds, derivatives of alkylaluminum compounds, halogenatedalkylaluminum compounds, and mixtures thereof for improved productselectivity, as well as improved catalyst system reactivity, activity,and/or productivity. Exemplary compounds include, but are not limitedto, triethylaluminum, tripropylaluminum, tributylaluminum,diethylaluminum chloride, diethylaluminum bromide, diethylaluminumethoxide, ethylaluminum sesquichloride, and mixtures thereof for bestcatalyst system activity and product selectivity. The most preferredalkylaluminum compound is triethylaluminum, for best results in catalystsystem activity and product selectivity.

Most preferably, the metal alkyl is a non-hydrolyzed alkylaluminumcompound, expressed by the general formula AlR₃, AlR₂ X, AlRX₂, AlR₂ OR,and/or Al₂ R₃ X₃, wherein R is an alkyl group and X is a halogen atom.Exemplary compounds include, but are not limited to, triethylaluminum,tripropylaluminum, tributylaluminum, diethylaluminumchloride,diethylaluminumbromide, diethylaluminumethoxide, diethylaluminumphenoxide, ethylaluminumethoxy-chloride, and/or ethylaluminumsesquichloride. Preferably, the metal alkyl is a trialkylaluminumcompound, AlR₃, and the most preferred trialkylaluminum compound istriethylaluminum, for reasons given above.

Usually, contacting and/or reacting of the chromium source,pyrrole-containing compound and a metal alkyl is done in an unsaturatedhydrocarbon. The unsaturated hydrocarbon can be any aromatic oraliphatic hydrocarbon, in a gas, liquid or solid state. Preferably, toeffect thorough contacting of the inorganic oxide, chromium source,pyrrole-containing compound, and metal alkyl, the unsaturatedhydrocarbon will be in a liquid state. The unsaturated hydrocarbon canhave any number of carbon atoms per molecule. Usually, the unsaturatedhydrocarbon will comprise less than about 70 carbon atoms per molecule,and preferably, less than about 20 carbon atoms per molecule, due tocommercial availability and ease of use. Exemplary unsaturated,aliphatic hydrocarbon compounds include, but are not limited to,ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof. The mostpreferred unsaturated aliphatic hydrocarbon compound is ethylene,because of elimination of catalyst system preparation steps and ethylenecan be a reactant. Exemplary unsaturated aromatic hydrocarbons include,but are not limited to, toluene, benzene, xylene, mesitylene,hexamethylbenzene, and mixtures thereof. Unsaturated, aromatichydrocarbons are preferred in order to improve catalyst systemstability, as well as produce a highly active and selective catalystsystem. The most preferred unsaturated aromatic hydrocarbon is toluene.

It should be recognized, however, that the reaction mixture comprising achromium source, pyrrole-containing compound, metal alkyl andunsaturated hydrocarbon can contain additional components which do notadversely affect and can enhance the resultant catalyst system, such as,for example, halides.

Catalyst Systems

Catalyst systems prepared in accordance with this invention can be usedolefin polymerization. Catalyst systems comprise a chromium source,pyrrole-containing compound, an unsaturated hydrocarbon and a metalalkyl, all supported on a support, as disclosed earlier. In accordancewith a second embodiment of this invention, these supported catalystsystems, which have not been activated in an oxygen-containing ambient,can have usefulness for other purposes. As used in this disclosure, anunactivated, supported catalyst system which has been used at leastonce, for another purpose, can be considered a waste chromium-containingcatalyst system.

The amount of chromium source, pyrrole-containing compound, unsaturatedhydrocarbon, metal alkyl, and support used to prepare a polymerizationcatalyst system can be any amount sufficient that, after activation andwhen combined with one or more olefins, polymerization occurs.Generally, the chromium component is used in an amount sufficient togive about 0.05 to about 5, preferably 0.1 to 2 weight percent chromium,based on the total weight of the chromium and support after activation.If necessary, chromium compound can be added to a support, or apreviously chromium compound impregnated support, in succession.Usually, successive impregnation is not preferred, but can be necessaryif a weak, i.e., dilute, chromium compound solution is used forimpregnation.

The catalyst system components can be combined in any manner underconditions suitable to form an effective catalyst system. Thepreparation of the catalyst system preferably occurs in the absence ofoxygen, which can deactivate the catalyst system, and under anhydrousconditions, i.e., in the initial absence of water. Therefore, a dry,inert atmosphere, such as, for example, nitrogen and/or argon, is mostpreferred.

The reaction pressure, during catalyst system preparation, can be anypressure which does not adversely affect the reaction. Generally,pressure within the range of from about atmospheric pressure to aboutthree atmospheres are acceptable. For ease of operation, atmosphericpressure is generally employed.

The reaction temperature, during catalyst system preparation, can be anytemperature. In order to effectuate a more efficient reaction,temperatures which maintain the reaction mixture in a liquid state, forreasons given above, are preferred.

The reaction time, during catalyst system preparation, can be any amountof time necessary for the reaction to occur. The reaction can beconsidered a dissolution process; any amount of time whereinsubstantially all soluble reactants can be dissolved is sufficient.Depending on the reactants, as well as the reaction temperature andpressure, reaction time can vary. Times of less than about 1 day can besufficient. Usually, reaction time is less than about 60 minutes. Underoptimum conditions, the reaction time can be within the range of fromabout 1 second to about 15 minutes. Longer times usually provide noadditional benefit and shorter times may not allow sufficient time forcomplete reaction.

A solid catalyst system can be recovered according to any method knownin the art. Recovery of a solid catalyst system can help reduce, oreliminate, the presence of any unsaturated hydrocarbon(s) which are notpolymerization reactants and can be polymerization reaction poisons. Forexample, aromatic hydrocarbons, such as, for example, excess toluene,can poison a polymerization reaction.

Preferably, a solid catalyst system is recovered by filtration andsubsequently washed with a sufficient amount of a saturated hydrocarbon.Saturated hydrocarbons useful for washing include, but are not limitedto, aliphatic hydrocarbons having from about 1 to about 20 carbon atomsper molecule. Preferably, that aliphatic hydrocarbon is a linearaliphatic hydrocarbon and has from 1 to 15 carbon atoms per molecule.Exemplary saturated hydrocarbons include, but are not limited to,methane, propane, butane, pentane, hexane, octane, and/or 1-decene.

After filtration, the polymerization catalyst system, preferably, can bewashed with a saturated hydrocarbon wash solution until a clear filtrateis observed. After washing, the solid catalyst system can be storedunder a dry, inert atmosphere until ready for activation. The resultingchromium component on the support is then subjected to activation in anoxygen-containing ambient in the manner conventionally used in the art.Because of economy, the preferred oxygen-containing ambient is air,preferably dry air. The activation is carried out at an elevatedtemperature for about one half to about 50 hours, preferably 2 to 10hours at a temperature within the range of 400° to 900° C. Under theseconditions, at least a substantial portion of any chromium in a lowervalent state is converted to the hexavalent form by this calcinationprocedure.

Optionally, the resulting calcined supported catalyst component iscooled and then subjected to at least partial reduction of thehexavalent chromium to a lower valent state prior to combining with thecocatalyst. The reducing agent must be carbon monoxide. The carbonmonoxide can be employed at temperatures between 300° to 500° C.although it is more often employed at temperatures in the range of about350° to 450° C. The partial pressure of the reducing gas in thereduction operation can be varied from sub-atmospheric pressures torelatively high pressures, but the simplest reducing operation is toutilize essentially pure carbon monoxide at about atmospheric pressure.

The reduction time can vary from a few minutes to several hours or more.The extent of reduction can be followed by visual inspection of catalystcolor. The color of the initial activated catalyst is generally orange,indicating the presence of hexavalent chromium. The color of the reducedcatalyst employed in the invention is blue, indicating that all orsubstantially all of the initial hexavalent chromium has been reduced tolower oxidation states, generally the divalent state.

The course of the reduction of the air-activated orange catalyst withcarbon monoxide can be determined exactly by pulse titration. A knownamount of carbon monoxide is added per pulse and the amount of evolvedcarbon dioxide is measured. When reduction is complete, only carbonmonoxide will be present and the catalyst is blue in color. The reducedblue catalyst can be titrated with pulses of oxygen to convert thecatalyst to the original orange color. When oxidation is complete,oxygen will be evident in the offgas.

After reduction, the reduced supported catalyst component is cooled toabout room temperature, e.g. 25° C. in an inert atmosphere such as argonor nitrogen to flush out the carbon monoxide. After this flushingtreatment, the catalyst is kept away from contact with either carbonmonoxide or oxygen.

Cocatalysts

Catalyst systems of this invention can be used in conjunction with acocatalyst if desired. Suitable Cocatalysts include, but are not limitedto, aluminum and boron alkyls, which if used, can increase the melt flowcharacteristics of the resultant polymer. The most preferred boroncompounds are trihydrocarbyl boron compounds, particularlytri-n-butylborane, tripropylborane, and triethylborane (TEB). Othersuitable boron compounds include trialkyl boron compounds broadly,particularly those having alkyl groups of about 1 to about 12 carbonatoms, preferably, about 2 to about 5 carbon atoms; triaryl boroncompounds such as triphenylborane; boron alkoxides such as B(C₂ H₅)₂ OC₂H₅ ; and halogenated alkyl boron compounds such as BC₂ H₅ Cl₂. Suitablealuminum alkyls include R'₃ Al,R'₂ AlX and R'AlX₂ compounds where R' isa hydrocarbyl radical with about 1 to about 12 carbon atoms and X is ahalogen, preferably chlorine. Triethylaluminum and diethylaluminumchloride are particularly suitable.

The cocatalyst is used in an amount within the range of about 0.1 toabout 1000, preferably about 0.25 to about 100, parts per million basedon the solvent or diluent in systems employing a solvent or diluent andbased on total reactor contents in systems not employing a solvent ordiluent. Based on the chromium in the catalyst, they are used in anamount so as to give about 0.05 to about 1000, preferably about 0.05 toabout 300 times as much aluminum by weight as chromium by weight. Basedon atoms of boron per atoms of chromium, the amount of cocatalyst usedwill give about 0.5 to about 500, preferably about 1 to about 100, atomsof boron (or aluminum) per atom of chromium.

The cocatalyst can be either premixed with the catalyst system orintroduced into the reactor as a separate stream, the latter being thepreferred procedure for ease of catalyst system preparation andhandling.

Of course, the final catalyst can be used with, or contain, otheringredients which do not adversely affect its performance, as forexample other cocatalyst, antistatic aids in the polymerization zone,and other conventional ingredients.

Reactants

Reactants applicable for use with the catalyst systems and processes ofthis invention are olefinic compounds which can polymerize, i.e., react,with other olefinic compounds. The catalyst systems of the invention canbe used to polymerize at least one mono-1-olefin having 2 to about 10carbon atoms per molecule. Exemplary compounds include, but are notlimited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and1-octene.

This invention is of particular applicability in producing ethylenehomopolymers and copolymers from mixtures of ethylene and about 0.5 toabout 20 mole percent of one or more comonomers selected from 1-olefinshaving about 3 to about 20 carbon atoms per molecule. Exemplarycomonomers include, but are not limited to, aliphatic 1-olefins, such aspropylene, 1-butene, 1-pentene, 1-hexene, 1-octene and other higherolefins and conjugated or non-conjugated diolefins such as1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-l,3-butadiene,1,4-pentadiene, 1,7-hexadiene, and other such diolefins and mixturesthereof. Ethylene copolymers preferably constitute at least about 90,preferably about 97 to about 99.6 weight percent polymerized ethyleneunits. Propylene, 1-butene, 1-pentene, 1-hexene and 1-octene areespecially preferred comonomers for use with ethylene.

The presence of comonomer has a tendency to increase melt flow more thanwould be expected. Hence, the use of only a small amount of comonomer,say 0.001 to 0.3, preferably 0.01 to 0.1, mole percent in the feed canbe used to give a polymer which is essentially a homopolymer but whichhas increased melt flow.

Reaction Conditions

The polymers can be prepared from catalyst systems of this invention bysolution polymerization, slurry polymerization, and gas phasepolymerization techniques using conventional equipment and contactingprocesses. Contacting of the monomer or monomers with the catalystsystem can be effected by any manner known in the art of solidcatalysts. One convenient method is to suspend the catalyst system inthe organic medium and to agitate the mixture to maintain the catalystsystem in suspension throughout the polymerization process. Other knowncontacting methods such as fluidized bed, gravitating bed, and fixed bedcan also be employed. Catalyst systems of this invention are especiallyuseful in a particle form process as disclosed in Witt, U.S. Pat. No.3,724,063, the disclosure of which is hereby incorporated by reference.

The catalyst systems of this invention are particularly suitable for usein slurry polymerizations. The slurry process is generally carried outin an inert diluent (medium), such as paraffin, cycloparaffin oraromatic hydrocarbon. For predominantly ethylene polymers, temperatureswithin a range of about 66° to about 110° C. are employed.

The medium and temperature are selected such that the polymer isproduced as solid particles and is recovered in that form. Pressures inthe particle form process can vary from about 110 to about 700 psia(0.76-4.8 MPa) or higher. The catalyst system is kept in suspension andis contacted with the amount or monomers at sufficient pressure tomaintain the medium and at least a portion of the monomer or monomers inthe liquid phase.

Generally in slurry polymerization of ethylene homopolymer andpredominantly ethylene copolymer systems, the feasible temperature rangeis about 93° to about 110° C. Commercial systems are operated as closeto the maximum as possible, i.e., about 107°±3° C., in order to obtainthe highest possible melt index without the polymer going into solution.Depending on the choice of catalyst system support, some catalystsystems of this invention allow operating at the low end to this range,i.e., about 96±3° C., in systems normally employing a temperature ofabout 107° C. The lower temperature gives a relatively higher monomerpartial pressure, thus giving higher activity.

Hydrogen can be added to the reactor to control the molecular weight ofthe polymer. Generally, hydrogen concentration is inversely proportionalto the molecular weight of the polymer, i.e., increasing hydrogenpressure decreases the polymer molecular weight. In prior art, hydrogenis generally used at pressures up to about 120 psig (0.8 MPa),preferably within the range of about 20 to about 70 psig (about 0.01 toabout 0.48 MPa). Similar amounts can be used in accordance with thisinvention although smaller amounts are sometimes preferred because ofthe sensitivity of this catalyst system to the effects of hydrogen.

EXAMPLES

In the following Examples, all catalyst systems were prepared under drynitrogen, at ambient temperature and pressure, unless otherwiseindicated. Catalyst supports were either aluminophosphate, prepared inaccordance with U.S. Pat. No. 4,364,855, herein incorporated byreference, activated at 700° C., with a P/Al molar ratio of 0.4; or asilica-titania cogel, prepared in accordance with U.S. Pat. No.3,887,494, herein incorporated by reference, dried at 200° C. undernitrogen, prior to use.

The catalyst system used in Run 101 was prepared by combining 10.1 galuminophosphate, 37 ml of 1M triethylaluminum (TEA) in hexanes, and 150ml toluene. The slurry was stirred for about 24 hours. Then, 1.1 g of achromium pyrrolide complex ([Na(DME)₂ ][CrCl(C₄ H₅ N)₃ (DME)]) (CrPy₃),wherein DME is dimethoxyethane, was added; the slurry was stirred forabout 24 hours and filtered. The solid was washed, first with tolueneand then with pentane until a clear filtrate was observed. The solidproduct was dried and then calcined, or activated, in air at 850° C. for3 hours.

The catalyst system used in Runs 102 and 103 was prepared by combining2.0 g aluminophosphate, 6 ml of 1.9M TEA in toluene, 15 ml toluene and0.202 g CrPy₃. The slurry was stirred for about 48 hours. The slurry wasfiltered and the solid was washed twice with toluene and then twice withpentane until a clear filtrate was observed. All of the filtrate, whichwas a dark brown color, was saved and can be referred to as a typicalsolution of a waste chromium compound.

Then, 5.1 g of silica-titania cogel was added to the waste chromiumcompound solution and the slurry was allowed to stand for about 16hours. The solution decolorized. The slurry was filtered and the solidwas washed twice with toluene and then twice with pentane until a clearfiltrate was observed. The final solid product was dried and calcined,or activated, in air at 850° C. for 3 hours. The calcined, solid productwas orange in color.

The polymerization runs were carried out in a two liter reactor underslurry (particle form) conditions. The diluent was isobutane and reactortemperature was 90° C. Reactor pressure was held at 550 psig during thepolymerization, with ethylene being fed on demand.

The actual charging of the reactor was accomplished by purging thereactor at 100° C. with a stream of nitrogen for at least 15 minutes,the reactor temperature was lowered to 90° C. and a preweighed amount ofsupported catalyst system and 0.5 ml of a one (1) weight percent, basedon the amount of isobutane, triethylboron (TEB) cocatalyst were chargedagainst a slight countercurrent of nitrogen. One liter of isobutane wasthen charged to the reactor and finally the reactor pressurized withethylene. The reaction time was one hour.

The ethylene consumed was determined using a precalibrated ethylene flowmeter. Solid products were obtained by venting the reactor to atmosphereand collecting the solid material. The solids were dried at 100° C. in avacuum oven and weighed. The yield of solid product was obtained byweighing the combined solid and catalyst residues and subtracting fromthis the preweighed catalyst charge.

Polymer analyses were conducted according to the following procedures:

Density (g/cc): ASTM D1505-68 and ASTM D1928, Condition C. Determined ona compression molded sample, cooled at about 15° C. per minute, andconditioned at room temperature for about 40 hours.

High Load Melt Index (HLMI)(g/10 min): ASTM D1238. Determined at 190° C.with a 21,600 gram weight.

Melt Index (MI)(g/10 min): ASTM D1238. Determined at 190° C. with a2,160 gram weight.

The heterogeneity index (Mw/Mn), which is the weight average molecularweight (Mw) divided by the number average molecular weight (Mn), wasdetermined using data collected by gel permeation chromatography. Thisgel permeation chromatography was accomplished with a Waters Cchromatograph at 140° C. with 1,2,4 -trichlorobenzene as a solvent.

The results of the polymerization reactions are in Table I, below.

                  TABLE I                                                         ______________________________________                                                Run        Run      Run                                                       101        102      103                                               ______________________________________                                        Catalyst  0.1215       0.0702   0.1490                                        Charge, g                                                                     Solid product                                                                           196.7        47       288                                           Yield, g                                                                      Activity, 1590         1340     2000                                          g/polymer/                                                                    g catalyst/hr                                                                 Density, g/cc                                                                           0.958        ND       0.964                                         MI,       0            ND       0.77                                          g/10 min                                                                      HLMI,     0.17         ND       49.5                                          g/10 min                                                                      Weight Avg.                                                                             414,000      ND       171,800                                       Molecular                                                                     Weight, Mw                                                                    Number Avg.                                                                             11,400       ND       11,300                                        Molecular                                                                     Weight, Mn                                                                    Heterogeneity                                                                           36.2         ND       15.2                                          Index, Mw/Mn                                                                  ______________________________________                                         a) ND means not determined.                                              

The results in Table I show that waste-chromium-containing solutioncomprising a chromium-containing compound, a pyrrole-containing compoundand an unsaturated hydrocarbon, and a metal alkyl can be supported on aninorganic oxide and activated to form an active polymerization catalystsystem.

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to prepare a catalyst systemcomposition comprising:a) contacting a waste chromium compound, whichhas been previously used for another purpose and subsequently recovered,wherein said waste chromium compound comprises a chromium-containingcompound, a pyrrole-containing compound, an unsaturated hydrocarbon; anda non-hydrolyzed aluminum alkyl; and a support selected from the groupconsisting of zeolites, inorganic oxides, and mixtures thereof; b)recovering a solid product; c) activating said solid product in thepresence of oxygen at a temperature within a range of about 400° toabout 900° C.; and d) recovering a solid catalyst system.
 2. A processaccording to claim 1 wherein said waste chromium compound is a filtraterecovered following a process to prepare a supported chromiumpyrrolide-based catalyst system.
 3. A process according to claim 1wherein said waste chromium compound is a previously used, uncalcinedinorganic oxide supported chromium pyrrolide-based catalyst system.
 4. Aprocess according to claim 1 wherein said chromium compound is selectedfrom the group consisting of chromium(II)-compounds,chromium(III)-compounds, and mixtures thereof.
 5. A process according toclaim 4 wherein said chromium compound is a chromium(II)-compoundselected from the group consisting of chromous bromide, chromousfluoride, chromous chloride, chromium(II) bis(2-ethylhexanoate),chromium(II) acetate, chromium(II) butyrate, chromium(II) neopentanoate,chromium(II) laurate, chromium(II) stearate, chromium(II) oxalate,chromium(II) pyrrolides, and mixtures of two or more thereof.
 6. Aprocess according to claim 4 wherein said chromium compound is achromium (III) compound is selected from the group consisting ofchromium(III) 2,2,6,6,-tetramethylheptanedionate [Cr(TMHD)₃ ],chromium(III) 2-ethylhexanoate [Cr(EH)₃ ], chromium(III) naphthenate[Cr(Np)₃ ], chromium(III) chloride, chromium(III)tris(2-ethylhexanoate), chromic bromide, chromic chloride, chromicfluoride, chromium(III) oxy-2-ethylhexanoate, chromium(III)dichloroethylhexanoate, chromium(III) acetylacetonate, chromium(III)acetate, chromium(III) butyrate, chromium(Ill) neopentanoate,chromium(III) laurate, chromium(III) stearate, chromium (III)pyrrolides, chromium(III) oxalate, and mixtures of two or more thereof.7. A process according to claim 1 wherein said pyrrole-containingcompound has from about 1 to about 20 carbon atoms per molecule.
 8. Aprocess according to claim 7 wherein said pyrrole-containing compound isselected from the group consisting of hydrogen pyrrolide (pyrrole),lithium pyrrolide, sodium pyrrolide, potassium pyrrolide, cesiumpyrrolide, salts of substituted pyrrolides, and mixtures of two or morethereof.
 9. A process according to claim 8 wherein saidpyrrole-containing compound is a salt of a substituted pyrrolide and isselected from the group consisting of pyrrole-2-carboyxlic acid,2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydroindole,2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole,3-acetyl-2,4-dimethylpyrrole,ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrroleproprionate,ethyl-3,5-dimethyl-2-pyrrolecarboxylate, and mixtures of two or morethereof.
 10. A process according to claim 1 wherein said unsaturatedhydrocarbon has less about 70 carbon atoms per molecule, and is selectedfrom the group consisting of unsaturated aromatic hydrocarbons,unsaturated aliphatic hydrocarbons, and mixtures thereof.
 11. A processaccording to claim 10 wherein said unsaturated hydrocarbon is anunsaturated aromatic hydrocarbon selected from the group consisting oftoluene, benzene, xylene, mesitylene, hexamethylbenzene, and mixtures oftwo or more thereof.
 12. A process according to claim 11 wherein saidunsaturated aromatic hydrocarbon is toluene.
 13. A process according toclaim 10 wherein said unsaturated hydrocarbon is an aliphatichydrocarbon selected from the group consisting of ethylene, 1-hexene,1,3-butadiene and mixtures of two or more thereof.
 14. A processaccording to claim 13 wherein said unsaturated aliphatic hydrocarbon isethylene.
 15. A process according to claim 1 wherein said inorganicoxide is selected from the group consisting of silica, silica-alumina,alumina, fluorided, alumina, silated alumina, thoria, aluminophosphate,aluminum phosphate, phosphated silica, phosphated alumina,silica-titania, coprecipitated silica/titania, fluorided/silatedalumina, and mixtures thereof.
 16. A process according to claim 15wherein said inorganic oxide support is aluminophosphate.
 17. A processaccording to claim 1 wherein said non-hydrolyzed aluminum alkyl isselected from the group consisting of triethylaluminum,tripropylaluminum, tributylaluminum, diethylaluminumchloride,diethylaluminumbromide, diethylaluminumethoxide, diethylaluminumphenoxide, ethylaluminumethoxy-chloride, ethylaluminum sesquichloride,and mixtures of two or more thereof.
 18. A process according to claim 17wherein said non-hydrolyzed alkyl aluminum compound is triethylaluminum.19. A process to prepare a catalyst system composition comprising:a)contacting a waste chromium compound, which has been previously used foranother purpose and subsequently recovered, wherein the waste chromiumcompound is a chromium pyrrolide comprising 2,5-dimethylpyrrole;toluene; and non-hydrolyzed triethylaluminum; and an aluminophosphatesupport; b) recovering a solid product; c) activating said solid productin the presence of oxygen at a temperature within a range of about 400°C. to about 900° C.; and d) recovering a solid catalyst system.